New vat dyestuffs of the anthraquinone series



NEW VAT DYESTUFFS or THE ANTI-IRA- QUINONE SERIES Willy Braun,Heidelberg, and Wilhelm Ruppel, Mannheim-Kaefertal, Germany, assignorsto Badische Anilm- & Soda-Fabrik Aktiengesellschaft, Rhineland-Pfalz,Germany No Drawing. Application January 28, 1958 Serial No. 711,569

Claims priority, application Germany April 26, 1957 6 Claims. (Cl.260-3075) This invention relates to a process for the production of vatdyestuffs of the anthraquinone series and to new vat dyestuffs of theanthraquinone series.

In the US. patent specifications Nos. 2,147,569 and 2,244,655 there isdescribed, inter alia, the production of1.4-diamino-2-anthraquinonyl-anthraquinone-oxazoles in which the4-position amino group is acylated in different Ways. These compounds,when the amino group is acylated by benzoic acid, monohalogenbenzoicacids or trifluoromethylbenzoic acids, are blue vat dyestuffs fast tochlorine which however cannot be discharged pure white.

It is therefore the object of this invention to find new blue vatdyestuffs fast to chlorine which can be discharged pure white.

We have now found that vat dyestuffs of this series which can bedischarged white and moreover are faster can be prepared by acylating a1.4-diamino-2-anthraquinonyl-anthraquinone-oxazole of the generalformula O NHg I with a reactable compound containing the group CO.A inwhich A is a phenyl radical bearing at least two halogen atoms selectedfrom the group consisting of polyhalogenbenzoic acids,polyhalogenbenzoic acid halides and polyhalogenbenzoic acid anhydrides.

As 1.4-diamino-2-anthraquinonyl-anthraquinone-oxazoles of the formula Ithere may be mentioned for example1.4-diamino-2-anthraquinonyl-2.3'-anthraquinoneoxazole and1.4-diamino-2-anthraquinonyl-1'(N).2-anthraquinone-oxazole, and asreactive compounds which contain the group CO.A in which A is a phenylradical hearing at least two halogen atoms there may be mentionedcarboxylic acids, carboxylic acid anhydrides and carboxylic acidchlorides in which A represents the radical of a di-, tri-, tetraorpenta-halogenbenzene, such as a chloro-, bromoor chlorobromobenzene, forexample a dichlorobenzene, a dibrornobenzene, amonochloromonobromobenzene, a trichlorobenzene, a dichloro-mono- 02,905,691 C6 Patented Sept. 22, 1959 bromobenzene, a tetrachlorobenzeneor a pentachloro benzene. Y

The new dyestuffs of the formula in which A is a penyl radical hearingat least two halogen I atoms are distinguished from the known dyestuffsnot only by their white dischargeability but also by a displacement ofthe shade of color towards violet which is i very desirable tinctoriallyand also by considerably better wet fastness.

For the production of the new dyestuffs, for example the acid chlorideof a polyhalogenbenzoic acid may be:

allowed to act on a suspension of a 1.4-diamino-2-an-- thraquinonylanthraquinone-oxazole in an organic solvent, such as nitrobenzene, attemperatures of about 120 to 220 C., advantageously about 140 to 180 C.,or

the polyhalogenbenzoic acid is brought to reaction t0-- gether with theanthraquinone-oxazole and the amount of.

thionyl chloride necessary for the conversion of the carboxylic acidinto the acid chloride. In this way the: preparation of the acidchloride is combined with theacylation of the1.4-diamino-2-anthraquinonyl-anthra-- quinone-oxazole.

The following polyhalogenbenzoic acids and/or their. halides oranhydrides are for example suitablev forthe: preparation of the newdyestufis: 2.5-dichlorobenzoic: acid, 2.5-dibromobenzoic acid,3.4-dichlorobenzoic acid, 2-chlor-5-bromobenzoic acid,2.4-dichlorobenzoicacid, 2.4.5-trichlorobenzoic acid,2.5.4-dichlorobromobenzoic acid and also tetrachloroorpentachloro-benzoic acids.

The new dyestufi's can be used for coloring cellulose fibers, such ascotton and rayon.

mixture is then heated While stirring well for 5 hours at The followingexamples will further illustrate this invention but the invention is notrestricted to these examples. The parts specified in the examples areparts by weight.

Example 1 nitrobenzene; then 54 parts of 2.5-dichlorobenzoyl chlorideare introduced and 6 parts of pyridine added. The

to C. and another hour at C. After cooling to 100 C. it is filtered bysuction, covered with warm nitrobenzene and the filter cake freed fromnitrobenzene by steam distillation. After drying there are obtainedabout 110 parts of a violet vat dyestulf. The dyeings prepared with thedyestutf in the usual way are completely fast to chlorine, have verygood wet fastness and may be discharged pure white.

bromobenzoic acidchloride for the acylation,

A very similar dyestulf is obtained by using '2.5-di- 3 Example '2 Byusing the same amount of 3.4-dichlorobenzoyl chlo ride instead of the2.5-dichlorobenzoyl chloride used in Example 1 there is obtained in thesame yield a vat dyestufi which goes onto cotton in very reddish blueshades; it has the same valuable fastness properties and may also bedischarged pure white.

The 3.4-dichlorobenzoyl chloride may also be replaced by 94 parts of3.4-dichlorobenzoic acid anhydride.

Example 3 10 parts of1.4-diamino-2;anthraquinonyl-2.3'-anthraquinone-oxazole, 6 parts of3i4-dichlorobenzoic acid, 0.6

part-of pyridine and Sparts'bf thionyl chloride areimro It is thenheated duced into 100 parts of nitrobenzene. for 3 hours at 100 C.,onehour' at 120 C.', S'hours at 145 to 150 C. and another hour at 180 C.It is then allowed to cool, filtered by suction at 120 C., covered withhot nitrobeniene, washed with benzene and dried. About 11.5 parts of adyestufi are obtained which agrees with that obtainable according toExample 2.

Example 4 v1'00 parts of 1.4diamino-2-anthraquinonyl-2'.3'-anthraquinone-oxazole are heated with1,000 parts of nitrobe'nzene at 120 C. Then 65 parts of2.5-chlorobromobenzoyl chloride :are introduced and 6 "parts 'of'pyridine added.- The, mixture is heated'while" stirring well for. 5hours git-145 to150" C.,and foranotherhour at'180" C.- After coolingvto100 .C.; itis workedru'p as inEx ample- 1. Ablue violet 1vat dyestuifwith the same valuable properties as that obtained according to Example1 is obtained.

Example 5 whim-0120b i P s of '2A- dichlorobenzoyl' chloride 1 8-fpyridine arefintroduce'd. The? mixture-i uana while stirring forfourhoursat 145 to150 6., ai'1'd Hen-remembe pan-a 180? C Ami cooling'to100* 6. it is filtered bysuctionj'and the dye benjz'oylchlbride areintroduced; 6 parts otfpy riiliii f added andtlien'iixture heatdwhilestirring well fo 5' hours."

A ver'3i simila'r dyestufiis formed'by using theequi va' lent amount of2.5.4-dichlorobromobenzoyl chlorideas acylating agent.

- Example '7 100 parts of 1.4 diarnino-2-anthraquinonyl-1'(N) .2'oxazole areheated ;000 parts ofnitrobenzene to 120 C? The'n' 6 0parts of2:5-dichlorobenz0yl' chloride are introduced and theniixture heated withpowerful stirring foi'ft'hours at'145." to 150? C. and'another 2 hoursat 180 C5 Afte'r'cooling to 100 C., the dyestufif formed benzene',"freedby steaindistillation from adherent 'nitfo benzene and dried." About 120parts o'f a reddish blue vat dyestuffjare "obtained'whichhas the Sa evaluable piopf erties asthe'dye'st'uffs described inthe-foregoingexamples A very .similar 'dyestutf is obtained, byusing2.4.5-trichlorbenzoylichlbride for the acylation.

What we claim is:

1. A process for the production of vat dyestuifs of the anthraquinoneseries which comprises acylating a 1.4-diamino2-anthraquinonyl-anthraquinone-oxazole of the 5 general Formula I0 o IITH; /o A Q N Y I 0 NH: with a reactive compound which contains thegroup CO.A in which A represents a phenyl radical hearing at leasttwohalogen atoms and selected from the group consistiiig' ofpolyhalogenbenzoic acids, polyhalogenbenzoic acid halides andpolyhalogenbenzoic acid anhy'dride's. 1

2; A va-ayasme dr theg'enera Formula 11' o NH-CO Q i 1;

in'which A is a phenyl radical hearing at least two halogen atoms. v

3. A' vatdyestufi'of the general formula in which A is a phenyl radicalcontaining at least two halogen atoms.

4. The vat dySfifif Of the formula.

6. The vat dyestufi of the formula 0 0 NH, 0 I

0 NH-OO References Cited in the file of this patent UNITED STATESPATENTS Berthold et a1 Feb. 14, 1939 Holbro et a1. Sept. 24, 1957FOREIGN PATENTS Germany Feb. 28, 1936 UNITED STATES PATENT OFFICECertificate of Correction Patent No. 2,905,691 September 22, 1959 WillyBraun et a1.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 4, lines 55 to 60, claim 4, for that portion of the formulareading read C1 C1 Signed and sealed this 14th day of June 1960.

Attest: KARL H. AXLINE, ROBERT C. WATSON,

Attestz'ng Ofiiaer. OOM/mz'ssiomr of Patents.

2. A VAT DYESTUFF OF THE GENERAL FORMULA II